Strontium and barium substituted lanthanum phosphate phosphors



Patented nately, the two alkaline-earths may be mixed together. 3,422,024 For actual specific examples, reference is made to the STRONTIUM AND BARIUM SUBSTITUTED fiOlloWing Table I. Other chemicals containing the essen- LANTHANUM PHOSPHATE PHOSPHORS William A. McAllister, Morristown, Pa., assignor to Westinghouse Electric Corporation, Pittsburgh, Pa., a corporation of Pennsylvania tial matrix and activator materials are, of course, usable. The raw mix is fired at temperatures in the range 1100- 1300 C., for example, in air, nitrogen or nitrogen-hydro- 524 816 gen mixtures for periods of up to several hours, two hours U g{ ci z gg 3o ifig Feb 1966 Ser No 4 blaims being preferred. The firing conditions, and particular alka- CL 09 04 line-earth used, determined the emission color and crystal 10 structure of the final product. The important gram-atom This invention relates to phosphor material and, m re ratios and firing conditions are summarized in Table I.

particularly, to phosphor material which efficiently gen- White oxides are used here as sources of europium and crates visible radiations of varying colors. lanthanum, nitrates, oxalates and other salts are equally Fluorescent lamps utilize phosphors which efficiently usable. Similarly phosphates other than the ammonium convert ultraviolet radiations of a wavelength of 254 nm. dihydrogen material are good sources of phosphate.

TABLE I Composition (moles) Gram-atom ratio Emission color for A excitation ofalkaline- Firing *4 1 3203 NHH PO; 1.1 00 EurOa Other earth metal to 254 nm. 365 nm. atmosphere lanthanum 1. 0 0.05 0.05 0.07, SrGOa 1213.3 Red Orange-red Air, N2.

1,0 0. 05 0. 05 0-40, SICOs Red -d0 All, N2.

1.0 0.05 0.05 0.875, SIC 3.. Blue-violet Blue Nfi-Hz.

1.0 0.05 0.05 0.70, 1 8 03-. Red Orange-red Air, N2.

1.0 0. 05 0. 05 0.07, Bacoiu Red Blue Nr+H into visible radiations. Other types of discharge devices The color of the light emitted by the resulting phosphor utilize phosphors which efiiciently convert both short may be varied by varying the gram-atom ratio between wavelength and long wavelength ultraviolet radiations the strontium (or barium) matrix component and the (such as those having a wavelength of 254 and 365 nm.) lanthanum matrix component. U.S. Patent No. 3,211,666, into visible radiations. Phosphors which emit in the red dated Oct. 12, 1965 describes a lanthanum phosphate region of the visible spectrum are particularly useful in phosphor having a long wavelength emission color which discharge devices and can be blended with other phosphors can be varied somewhat by the selection of the activator in order to achieve a desired color for the discharge deand the concentration thereof used. In the present phospor vice. Phosphors which are excited by ultraviolet radiations the emission color is varied by varying the strontium or to emit both in the short wavelength and long wavelength barium proportions relative to the lanthanum. At low regions of the visible spectrum are particularly useful. In concentrations of strontium (1 Sr:13.3 La) the emission addition, phosphors which are excited by ultraviolet nadicolor is red and orange-red respectively under 254 and ations to emit visible radiations both as a line emission 365 nm. excitation. At high concentrations of strontium and as a band emsission are particularly useful. (6.7 Sr:1 La), the air and/or nitrogen firings also give It is therefore an object of this invention to provide red emission under both long and short ultraviolet excitanovel phosphor material which efficiently converts ultration. Introduction of hydrogen into the firing atmosphere violet radiations into visible radiations. changes the emission of the resulting phosphor to blue It is a further object to provide phosphor material violet and blue. The response to 365 nm. exitation is excelhaving an emission color which can be varied 'by varying lent. the phosphor components, the relative gram-atom ratios In the barium-containing embodiment, for high Ba of the phosphor components, and the firing conditions. concentrations (2.34 Ba:1 La), the air and/or nitrogen It is an additional object to provide phosphor material fired phosphors also emit in the red and orange-red rewhich emits visible radiations with a spectrum consisting spectively under 254 and 365 nm. excitation wavelengths. of a series of lines or a combination of lines and a band. With Ba:La=1.l3:3, air and/ or nitrogen firing results in Briefly these and other objects which will become apa red-emitting phosphor. Addition of hydrogen to the parent as the description proceeds, are achieved 'by pronitrogen enhances the 254 nm. excited red emission and viding a phosphor composition having a matrix consisting also results in a blue band emission for 365 nm. excitation. essentially of (lanthanum, X) phosphate activated by Under simultaneous excitation by both 254 nm. and 365 europium, wherein X is at least one alkaline-earth metal nm., a composite red-line and blue band emission is obof the group consisting of strontium and barium. For 'best tained. performance the europium activator is supplemented by The ranges of gram-atom ratios of the total alkalinelithium, preferably in equal gram-atom amounts. The earth metal to the phosphorus in the phosphor are: emission color is varied by varying the amounts of the 0.05 /P 0 875 selected alkaline-earth (barium or strontium) employed vand relative to the lanthanum. 005 Ba/P O 7 As a specific example for preparing the strontium-containing embodiment of the present phosphor, the follow- At all concentrations of alkaline-earth, the sum of the ing components are thoroughly mixed to form a raw mix: gram-atom of alkaline-earths plus lanthanum is approxilanthanum oxide, ammonium dihydrogen phosphate, mately equal to the gram-atoms of phosphorus, that is, lithium carbonate, europium oxide, and strontium car- 'bonate. For the barium-containing embodiment, 'barium Wg car bonate is used instead of strontium carbonate. Alter- The emission of the phosphor includes a blue band when the phosphor is excited by long wavelength ultraviolet radiations, or when the phosphor is excited by a wide range of ultraviolet radiations which include long wavelength ultraviolet radiations, when the raw mix is fired in a slightly reducing atmosphere, and when:

As an example, suitable slightly reducing firing atmosspheres are a mixture of nitrogen with from 0.25% to 5% by volume of hydrogen added thereto. The amount of hydrogen used in the firing atmosphere can be varied from the foregoing example. The blue band emission is attributed to a reduction of some of the europium activator to the lower valence state.

Good phosphors can be obtained with other activator concentrations than those shown, e.g.

The red emission of (La, Ba)PO :Eu, Li under 254 nm. excitation is comparable to the corresponding LaPO :Eu, Li described in Patent No. 3,211,666. The blue emission of (La, Ba) PO :Eu, Li under 365 nm. excitation is better than the corresponding emission of CaSiO :Ce and approaches the emission of ZnS:Ag in brightness.

The best results occur when the europium and lithium activators are present in about equal gram-atom amounts. The preferred gram-atom ratio of Eu to the phosphorus in the phosphor is 0.1:1. As the gram-atoms of La decrease, the gram-atoms of alkaline-earth metal are increased to keep the gram-atom ratios of Sr+Ba+La/P equal to about 1.00.

After firing, the prepared phosphor is crushed into small particles. Refiring may be desirable to further the activation process or to increase the particle size of the phosphor crystals produced during firing.

When coating the phosphor onto lamp bulbs, it is desirable to limit the lehring temperatures which are normally required to volatilize organic binder materials. The phosphor of the present invention can readily be coated onto the lamp bulb by means of an electrostatic coating process, thereby precluding the necessity of using an organic binder material. With such a coating process, the maximum temperature to which the phosphor is exposed during lamp fabrication need not exceed about 450 C.

It will be recognized that the objects of the invention have been achieved by providing novel phosphor material which efliciently converts ultraviolet radiations into visible light. The color of the visible light is determined by the alkaline-earth used, and the relative amounts thereof to the phosphorus. A blue emission band may be achieved by firing the phosphor under slightly reducing conditions, In addition, the blue band may be provided to supplement the red emission spectrum.

Although this invention has been described with respect to preferred embodiments thereof, it is not to be so limited as changes and modifications may be made therein which are within the intended scope of the invention.

I claim as my invention:

1. A phosphor composition having a matrix consisting essentially of (lanthanum, X) phosphate, wherein X is at least one metal of the group consisting of strontium and barium, said matrix is activated by one of the group consisting of europium and europium plus lithium, and the ratio of metallic elements in said phosphor to phosphorus in said phosphor fall within the following gram-atom ranges:

and

X-l-La P and said phosphor is prepared by firing the phosphor raw mix in a slightly reducing atmosphere.

References Cited UNITED STATES PATENTS 3,211,666 10/1965 McAllister 252301.4

FOREIGN PATENTS 1,419,231 10/1965 France.

TOBIAS E. LEVOW, Primary Examiner.

R. D. EDMONDS, Assistant Examiner. 

1. A PHOSPHOR COMPOSITION HAVING A MATRIX CONSISTING ESSENTIALLY OF (LANTHANUM, X) PHOSPHATE, WHEREIN X IS AT LEAST ONE METAL OF THE GROUP CONSISTING OF STRONTIUM AND BARIUM, SAID MATRIX IS ACTIVATED BY ONE OF THE GROUP CONSISTING OF EUROPUM AND PLUS LITHIUM, AND THE RATIO OF METALLIC ELEMENTS IN SAID PHOSPHOR TO PHOSPHORUS IN SAID PHOSPHOR FALL WITHIN THE FOLLOWING GRAM-ATOM RANGES: 0.01<EU/P<0.24, 0<LI/P<0.24, 0.05<SR/P<0.875, 0.05<BA/P<0.7 AND (X+LA)/P=1 